The synthesis of
metal-redox active ligand complexes is described, along with reactivity studies
aimed at facilitating novel C-N bond forming reactions. A copper
bis(iminosemiquinone) structure is characterized, analyzed and its reduction
series are characterized and the reactivity of the Cu(II) bis(amidophenolate)
analog is investigated with tosyl azide. The identification of the major
reaction product and its characterization is detailed, with reaction
sensitivities and heavily distorted x-ray diffraction single crystal structure
generating a complex data set. The characterization of the isolated product is
ongoing, with EPR studies aimed at identifying the radical nature of the
complex. Unusual solvent effects and solubility issues have been noted with
these initial EPR studies and more data is necessary before analysis can be
properly attempted. An ytterbium bis(amidophenolate) complex was synthesized
and its reactivity studied with aryl azides. Initial reactivities generate the
first documented lanthanide tetrazenes in-lieu of the targeted ytterbium imido.
Reactivities and characterization of these complexes support a stable, heavily
ionic tetrazene-metal complex with no observed redox nature, UV light
sensitivities, or imido azide-tetrazene equilibrium observed in various
tetrazene transition metal complexes. Synthesis of a sterically blocked ytterbium
imido was attempted, utilizing DMAP. Initial isolation was achieved with
characterization and reactivity studies supporting the imido nature of the
complex. The weak coordinating of the DMAP provided instability that proved in
opposition to crystallization, however, so the imido could not be confirmed.
Initial reactions using alternative steric hinderance from triphenylphosphine
oxide and pyridine N-oxide prove promising to increasing the stability of the
presumed ytterbium imido. Organic synthesis was performed generating a
potential antibacterial agent. The synthesis of cyclopropenes was initiated as
antagonists for ETR proteins in fruits and plants. The intermediates proved
highly sensitive to harsh chemical conditions, which was overcome utilizing a
tin-mediated Barbier allylation. The cyclopropene alcohol synthon was
synthesized, though protecting group optimization is necessary.
| Identifer | oai:union.ndltd.org:purdue.edu/oai:figshare.com:article/15067494 |
| Date | 29 July 2021 |
| Creators | Matthew C Hewitt (11197530) |
| Source Sets | Purdue University |
| Detected Language | English |
| Type | Text, Thesis |
| Rights | CC BY 4.0 |
| Relation | https://figshare.com/articles/thesis/Redox_Active_Ligands_To_Facilitate_Reactivity_From_Redox_Restricted_Metals/15067494 |
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